DE1795845A1 - METHOD FOR MANUFACTURING THERMOPLASTIC COPOLYMERIZES FROM STYRENE AND FUMAR ACID ESTERS OF SECONDARY ALCOHOLS - Google Patents

METHOD FOR MANUFACTURING THERMOPLASTIC COPOLYMERIZES FROM STYRENE AND FUMAR ACID ESTERS OF SECONDARY ALCOHOLS

Info

Publication number
DE1795845A1
DE1795845A1 DE19641795845 DE1795845A DE1795845A1 DE 1795845 A1 DE1795845 A1 DE 1795845A1 DE 19641795845 DE19641795845 DE 19641795845 DE 1795845 A DE1795845 A DE 1795845A DE 1795845 A1 DE1795845 A1 DE 1795845A1
Authority
DE
Germany
Prior art keywords
styrene
acid esters
secondary alcohols
copolymerizes
ester
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
DE19641795845
Other languages
German (de)
Other versions
DE1795845C2 (en
DE1795845C1 (en
Inventor
Friedrich Dr Engelhardt
Wolfgang Dipl Chem Dr Tietz
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Wintershall Dea Deutschland AG
Original Assignee
Deutsche Texaco AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Publication of DE1795845C1 publication Critical patent/DE1795845C1/de
Application filed by Deutsche Texaco AG filed Critical Deutsche Texaco AG
Priority to DE19641795845 priority Critical patent/DE1795845C2/en
Priority claimed from DE19641795845 external-priority patent/DE1795845C2/en
Publication of DE1795845A1 publication Critical patent/DE1795845A1/en
Application granted granted Critical
Publication of DE1795845C2 publication Critical patent/DE1795845C2/en
Expired legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/06—Hydrocarbons
    • C08F212/08—Styrene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10—Esters
    • C08F222/12—Esters of phenols or saturated alcohols
    • C08F222/14—Esters having no free carboxylic acid groups, e.g. dialkyl maleates or fumarates

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Polymerisation Methods In General (AREA)

Description

Hamburg, den 28.4-. 1976 547/ikHamburg, April 28th. 1976 547 / ik

E 64 003 D Ausscheidung E 64 003 D elimination

DEUTSCHE TEXACO AKTIENGESELLSCHAFT 179 58 2000 Hamburg 13
Mittelweg 180DEUTSCHE TEXACO AKTIENGESELLSCHAFT 179 58 2000 Hamburg 13
Middle way 180

Verfahren zur Herstellung thermoplastischer Copolymerisate aus Styrol und Fumarsäureestern sekundärer AlkoholeProcess for the production of thermoplastic copolymers from styrene and fumaric acid esters of secondary alcohols

Ausscheidung aus P 15 20 702Eliminated from P 15 20 702

Es ist bereits bekannt, Vinylchloracetat in Masse, Lösung oder Dispersion zusammen mit Malein- und/oder Fumarsäureestern von linearen oder verzweigten primären, sekundären oder tertiären Alkoholen zu polymerisieren und dabei durch den Einsatz von Yinylchloracetat eine erhöhte Ausbeute zu erhalten.It is already known to use vinyl chloroacetate in bulk, solution or dispersion together with maleic and / or fumaric acid esters of linear or branched primary, secondary or tertiary alcohols to polymerize and thereby through the use of yinyl chloroacetate to obtain an increased yield.

Nach der DT-PS 1 176 8?1 werden thermoplastische Copolymerisate mit verbesserten Eigenschaften unter Verwendung von Estern <*,|3-ungesättigter Dicarbonsäuren nach dem Blockverfahren (Polymerisation in Substanz) in Gegenwart Radikale bildender Katalysatoren dann erhalten, wenn man als Ester Fumarsäureester sekundärer Alkohole verwendet.According to DT-PS 1 176 8-1, thermoplastic copolymers are used with improved properties using esters <*, | 3-unsaturated dicarboxylic acids according to the block method (Polymerization in bulk) in the presence of catalysts which form free radicals if the ester is fumaric acid ester secondary alcohols are used.

Es wurde nun gefunden, daß man zu gleichwertigen Copolymerisaten auch gelangen kann, wenn man an Stelle der Polymerisation in Substanz (Blockpolymerisation) andere an sich bekannte Polymerisationsmethoden, beispielsweise die Lösungs-, Suspensionsoder Emulsionspolymerisation anwendet. It has now been found that equivalent copolymers can also be obtained if the polymerization is used instead in substance (block polymerization) other known polymerization methods, for example, uses solution, suspension or emulsion polymerization.

Dies führt zu dem erheblichen Fortschritt, daß die Vorteile, die diese Polymerisationsverfahren gegenüber der PolymerisationThis leads to the considerable advance that the advantages that this polymerization process over the polymerization

- 2 6 0 9 8 4 8/0775 - 2 6 0 9 8 4 8/0775

in Substanz haben, wie leichtere Wärmeabfuhr während der Beaktion, Begrenzung der Viskosität, mit den hervorragenden Polymerisat- Eigenschaften, zu denen das Verfahren gemäß DTPS 1 176 871 führt, vereinigt werden. So lassen sich erfindungsgemäß Copolymerisate von Pumarsäureestern sekundärer Alkohole in kurzer Zeit und in sehr hohen Ausbeuten herstellen. in substance, like easier heat dissipation during the Response, limitation of the viscosity, with the excellent polymer properties, to which the method according to DTPS 1 176 871 leads to be united. Thus, according to the invention, copolymers of pumaric acid esters can be secondary Produce alcohols in a short time and in very high yields.

Die Erfindung sei an Hand der nachfolgenden Beispiele näher erläutert;The invention is explained in more detail with reference to the following examples;

Beispiel 1 (Copolymerisation in Suspension) Example 1 (copolymerization in suspension)

Nach dem an sich bekannten Verfahren der Suspensionspolymeri-™ sation werden folgende Ester gemeinsam mit Styrol im Gewicht sverhältnis 75 Teile Ester zu 25 Teilen Styrol copolymerisiert: According to the known method of Suspensionspolymeri- ™ The following esters are copolymerized together with styrene in a weight ratio of 75 parts ester to 25 parts styrene:

1. Fumarsäure-di-n-propylester,1. Fumaric acid di-n-propyl ester,

2. Fumarsäure-di-isopropylester.2. Fumaric acid diisopropyl ester.

Die Monomeren werden in der sechsfachen Menge Wasser unter Verwendung von 1 % tert.-Butylhydroperoxyd und 1 % Polyvinylalkohol bei 900C mittels Rühren in feiner Verteilung gehalten. Ergebnis:The monomers are kept finely divided in six times the amount of water using 1 % tert-butyl hydroperoxide and 1% polyvinyl alcohol at 90 ° C. by means of stirring. Result:

Ester 1 nach 72 Stunden zähe Masse, Ester 2 nach 72 Stunden harte, farblose Perlen.Ester 1 viscous mass after 72 hours, Ester 2 hard, colorless pearls after 72 hours.

Beispiel 2 (Copolymerisation in Emulsion) Example 2 (copolymerization in emulsion)

Nach dem Verfahren der Emulsionspolymerisation werden folgende Ester gemeinsam mit Styrol im Verhältnis Ester zu Styrol 75*25 copolymerisiert:According to the emulsion polymerization process, the following esters are used together with styrene in the ratio of ester to styrene 75 * 25 copolymerized:

1. Fumarsäure-di-n~propylester,1. Fumaric acid di-n ~ propyl ester,

2. Fumarsäure-di-isopropylester.2. Fumaric acid diisopropyl ester.

6098A 8 /077 56098A 8/077 5

BAD ORIGINALBATH ORIGINAL

— O ""- O ""

Die Monomeren werden in der dreifachen Menge Wasser unter Verwendung von 1 % Misodecylmaleinat-sulfonsaurem UTa und 0,3 % Wasserstoffperoxyd bei 900C mittels Rühren in Emulsion gehalten. Nach der Polymerisation werden die Emulsionen durch Zugabe von konzentrierter Salzsäure zerstört. Ergebnis:The monomers are maintained in the three times the amount of water using 1% Misodecylmaleinat-sulphonate UTA and 0.3% hydrogen peroxide at 90 0 C by means of stirring in emulsion. After the polymerization, the emulsions are destroyed by adding concentrated hydrochloric acid. Result:

Ester 1 nach 72 Stunden zähe Masse, Ester 2 nach ?2 Stunden festes, weißes Polymerisat.Ester 1 viscous mass after 72 hours, Ester 2 solid, white polymer after 2 hours.

609848/077 5609848/077 5

Claims (1)

Ausscheidung aus P 15 20 702Eliminated from P 15 20 702 PatentanspruchClaim Verfahren zur Herstellung thermoplastischer Copolymerisate aus Styrol und irunarsäureestern sekundärer Alkohole, dadurch gekennzeichnet, daß man die Copolymerisatknin Suspension oder Emulsion vornimmt .Process for the production of thermoplastic copolymers from styrene and irunaric acid esters of secondary alcohols, characterized in that the copolymer is carried out in suspension or emulsion . 609848/0775 Bad or,q,naL 609848/0775 Bad or, q, na L
DE19641795845 1964-06-27 1964-06-27 Process for the production of thermoplastic copolymers from styrene and fumaric acid esters of secondary alcohols Expired DE1795845C2 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
DE19641795845 DE1795845C2 (en) 1964-06-27 1964-06-27 Process for the production of thermoplastic copolymers from styrene and fumaric acid esters of secondary alcohols

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE1520702 1964-06-27
DE19641795845 DE1795845C2 (en) 1964-06-27 1964-06-27 Process for the production of thermoplastic copolymers from styrene and fumaric acid esters of secondary alcohols

Publications (3)

Publication Number Publication Date
DE1795845C1 DE1795845C1 (en)
DE1795845A1 true DE1795845A1 (en) 1976-11-25
DE1795845C2 DE1795845C2 (en) 1979-03-01

Family

ID=

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105085805A (en) * 2015-07-17 2015-11-25 中国石油天然气股份有限公司 Polystyrene dipropyl butenedioate as well as preparation method and application thereof
CN105085804A (en) * 2015-07-17 2015-11-25 中国石油天然气股份有限公司 Polystyrene butenedioic acid dibenzyl ester and preparation method and application thereof
CN105085808A (en) * 2015-07-17 2015-11-25 中国石油天然气股份有限公司 Polystyrene butenedioic acid dioctyl ester and preparation method and application thereof
CN105085806A (en) * 2015-07-17 2015-11-25 中国石油天然气股份有限公司 Polystyrene butylene dibutyl ester and preparation method and application thereof
CN105085807A (en) * 2015-07-17 2015-11-25 中国石油天然气股份有限公司 Polystyrene dimethyl butenedioate and preparation method and application thereof
CN105085811A (en) * 2015-07-17 2015-11-25 中国石油天然气股份有限公司 Polystyrene butenedioic acid dibromopropyl ester and preparation method and application thereof
CN105175630A (en) * 2015-07-17 2015-12-23 中国石油天然气股份有限公司 Polystyrene diethyl glutaconate and synthesis method and application thereof

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105085805A (en) * 2015-07-17 2015-11-25 中国石油天然气股份有限公司 Polystyrene dipropyl butenedioate as well as preparation method and application thereof
CN105085804A (en) * 2015-07-17 2015-11-25 中国石油天然气股份有限公司 Polystyrene butenedioic acid dibenzyl ester and preparation method and application thereof
CN105085808A (en) * 2015-07-17 2015-11-25 中国石油天然气股份有限公司 Polystyrene butenedioic acid dioctyl ester and preparation method and application thereof
CN105085806A (en) * 2015-07-17 2015-11-25 中国石油天然气股份有限公司 Polystyrene butylene dibutyl ester and preparation method and application thereof
CN105085807A (en) * 2015-07-17 2015-11-25 中国石油天然气股份有限公司 Polystyrene dimethyl butenedioate and preparation method and application thereof
CN105085811A (en) * 2015-07-17 2015-11-25 中国石油天然气股份有限公司 Polystyrene butenedioic acid dibromopropyl ester and preparation method and application thereof
CN105175630A (en) * 2015-07-17 2015-12-23 中国石油天然气股份有限公司 Polystyrene diethyl glutaconate and synthesis method and application thereof
CN105085807B (en) * 2015-07-17 2018-01-02 中国石油天然气股份有限公司 Polystyrene dimethyl butenedioate and preparation method and application thereof
CN105085806B (en) * 2015-07-17 2018-01-02 中国石油天然气股份有限公司 Polystyrene butylene dibutyl ester and preparation method and application thereof
CN105085811B (en) * 2015-07-17 2018-01-05 中国石油天然气股份有限公司 Polystyrene butenedioic acid dibromopropyl ester and preparation method and application thereof
CN105085808B (en) * 2015-07-17 2018-02-02 中国石油天然气股份有限公司 Polystyrene butenedioic acid dioctyl ester and preparation method and application thereof
CN105085804B (en) * 2015-07-17 2018-02-02 中国石油天然气股份有限公司 Polystyrene butenedioic acid dibenzyl ester and preparation method and application thereof

Also Published As

Publication number Publication date
DE1795845C1 (en)

Similar Documents

Publication Publication Date Title
DE974268C (en) Process for the bulk polymerization of styrene
DE1495822C3 (en) Process for the production of copolymers from vinyl esters and ethylene
DE4438706A1 (en) Soluble copolymers for hair cosmetics
DE943145C (en) Process for the production of copolymers
DE2829652A1 (en) METHOD FOR PRODUCING N-VINYLAMIDE POLYMERS
DE1770154A1 (en) Graft copolymers
DE706509C (en) Polymerization of vinyl compounds in the presence of polymerization retarders
DE1795845A1 (en) METHOD FOR MANUFACTURING THERMOPLASTIC COPOLYMERIZES FROM STYRENE AND FUMAR ACID ESTERS OF SECONDARY ALCOHOLS
DE1795845C2 (en) Process for the production of thermoplastic copolymers from styrene and fumaric acid esters of secondary alcohols
DE1595554B2 (en) PROCESS FOR THE PRODUCTION OF Aqueous POLYMERISATLATICES
DE1050062B (en) Process for the preparation of polyvinyl chloride resins suitable for plastisol formation
DE912152C (en) Process for the polymerization or copolymerization of polymerizable unsaturated organic compounds
DE1221450B (en) Process for the production of copolymers of acrylic acid esters
DE1520702B2 (en) PROCESS FOR MANUFACTURING THERMOPLASTIC HOMOPOLYMERIZED OR COPOLYMERIZED PRODUCTS USING FUMAR ACID ESTERS OF SECONDARY ALCOHOLS
DE1520703C3 (en) Process for the production of thermoplastic homo- or copolymers using fumaric acid ester !!
DE1520703B2 (en) PROCESS FOR THE MANUFACTURING OF THERMOPLASTIC HOMOPOLYMERIZED OR COPOLYMERIZED PRODUCTS USING FUMAR ACID ESTERS
EP0048842A2 (en) Process for producing vinyl-chloride polymers
DE1068888B (en)
DE942352C (en) Process for the production of copolymers
DE1026074B (en) Process for the radical polymerization of polymerizable unsaturated organic compounds in aqueous suspension or emulsion
DE1595621C3 (en) Process for the preparation of Vlnylchlorld-Äthylen-Copolymeri seeds
DE2013020A1 (en) Impact-resistant, transparent vinyl chloride polymers
DE944520C (en) Process for the production of acyl nitrile copolymers
DE2044655A1 (en) Ethylene copolymers - with alkenyl acetylenes prepn
DE1645212B2 (en) Process for the production of thermoplastic copolymers using fumaric acid esters

Legal Events

Date Code Title Description
BI Miscellaneous see part 2
8339 Ceased/non-payment of the annual fee